JPS63270313A - Composition for forming film and powder of metallic oxide of rare earth element - Google Patents

Abstract

PURPOSE:To improve stability of a coating solution and to enable formation of a transparent thin film having high uniformity and powder, by using a beta- diketone and a beta-diketoester of rare earth element as a rare earth element compound soluble in an organic solvent. CONSTITUTION:A composition to form a film and powder of the rare earth element oxide consists of a compound of rare earth element shown by general formula of formula I and an organic solvent. In the formula I, M is one or more rare earth element, R is 1-10C alkyl, Y is chelate ligand selected from a beta-diketone and a beta-diketoester of rare earth element shown by general formulas of formula II and formula III, m and n are 1 or 2 integer, respectively and m+n=3. In the formulas II and III, R<1> and R<2> are 1-6C alkyl, R<3> is H or 1-6C alkyl. The composition is applied to a substrate, calcined simultaneously or after coating to give a thin film of rare earth element oxide or the composition is sprayed in a hot atmosphere to give powder of rare earth element oxide.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention applies rare earth metals to the surfaces of substrates such as glass, metals, ceramics, semiconductors, heat-resistant plastics, etc., tubes, powders, fibers, and other objects of various shapes. The present invention relates to a composition for forming an oxide film and for forming a powder of the oxide.

Rare earth metal oxides are used alone or in combination with other metal oxides in the field of optical materials such as phosphors, lasers, ultraviolet absorbers, and optical filters.

Use as ceramics for electronic engineering in the field of electronic materials such as thermistors, varistors, gas sensors, temperature sensors, etc., use as additives for ceramics, etc., superconducting materials, catalysts for cranking, etc., catalysts for automobile exhaust gas treatment. The use of rare earth metal oxides in various fields is being considered, and new practical developments can be expected by forming rare earth metal oxide thin films on the surfaces of substrate tubes, powders, fibers, and various other forms.

[Prior art and its problems]

General methods for forming metal oxide thin films include CVD using a metal compound with an appropriate vapor pressure as a raw material, applying a solution containing the metal compound by spraying, dipping, spin coating, etc. There are also known methods for forming thin films under reduced pressure, such as coating methods that involve subsequent baking, PVD methods, sputtering, etc. Among them, CVD methods under normal pressure are used as spray methods, dipping methods, and spin code methods. These methods are superior in terms of productivity.

Spray, dip, and spray thin films of rare earth metal oxides.
The use of rare earth octanoates, tris alkoxides, etc. has been proposed as an attempt to create the product using a general coating and firing method, which involves firing simultaneously with spin coating or subsequent firing. The properties are poor, carbon tends to remain in the film after firing, and it has been difficult to obtain a high quality rare earth metal oxide thin film due to problems such as the wettability of the film with the substrate. Furthermore, when rare earth tris alkoxide is used, it has poor stability against humidity, and insoluble precipitates are likely to form in the coating solution or in the undried coating film, and the formed film often becomes cloudy, resulting in a uniform and transparent coating film. It was difficult.

[Points of view and knowledge related to solving problems] The present inventors
β-diketone and β-diketoester complexes of rare earth elements are used as rare earth compounds that are soluble in organic solvents, have better solution stability than tris alkoxides, and can be decomposed at lower temperatures than octoates. I paid attention.

[Means of problem solving]

These compositions consisting of rare earth compounds and organic solvents have excellent stability and operability during solution storage and normal handling, and can be heated to produce uniform and transparent rare earth oxidation at the same time as or after application to the substrate. A thin film of the substance is obtained.

[Structure of the invention]

According to the present invention, the general formula % formula % (1) M is at least one rare earth element, R is a C1-1° alkyl group, Y is represented by the general formula, and R1 and 82 are is a C1-1 alkyl group,
a chelating ligand selected from β-diketones in which R3 is hydrogen or a Ct-c alkyl group, or β-ketoesters of the general formula and in which R1, R2, R3 are as defined above, m and n are each an integer of 1 or 2, and m+n
Provided are compositions for forming rare earth oxide films and powders comprising:

In the composition of the present invention, rare earth elements include Sc, Y, and La.
, Ce, Pr, Nd, Sm, Eu, Gd,
Tb, Dy, Ho, Er, Tm, Yly, L
u and mixtures thereof. It is well known that these elements are very similar in chemical behavior and give rise to mixed compounds.

It is also well known that metal β-diketones and β-diketoester strands are soluble in almost all organic solvents.

The β-diketone or β-diketoester forceps in the composition of the present invention combine rare earth metal tris alkoxide with benzene,
Dissolved in an aromatic hydrocarbon such as toluene or a hydrocarbon such as pentane, n-hexane, or octane, and reacted by adding an equimolar amount of a β-diketone or β-ketoester such as acetylacetone or ethyl acetoacetate to the tris alkoxide. It is obtained by distilling and separating the alcohol produced in the second reaction and the solvent used. The composition of the present invention can be prepared by dissolving the rare earth compound thus obtained in an organic solvent.

Solvents that can be used for this purpose are those that have an affinity for the surface of the substrate and are easily dryable after application.

Such solvents include esters such as ethyl acetate and ethyl propionate, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol,
Butyl alcohol, isobutyl alcohol, 5ee-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, pentyl alcohol, octyl alcohol, etc.
General formula ROH (R is an alcohol represented by a saturated hydrocarbyl group having 1 to 10 carbon atoms; saturated hydrocarbons such as hexane, pentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; Examples include cyclic ethers such as tetrahydrofuran and dioxane, cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve, formamides such as dimethylformamide and diethyl formamide, and sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide.

These solvents may be used alone or in combination of two or more.

The concentration of the rare earth element complex in the rare earth metal oxide thin film forming composition of the present invention is 0.1 after conversion to the metal oxide.
Although it is desirable that the amount is from wt% to 10wt%, the coating method and the substrate on which the coating is applied can be appropriately selected depending on the film thickness and the like.

The composition of the present invention is applied to a substrate and fired at the same time as or after the application to provide a rare earth element oxide thin film.

In order to bake simultaneously with coating, the substrate may be heated to a baking temperature and the complex solution may be applied to the surface by spraying or the like.

Moreover, a rare earth element oxide powder can also be obtained by spraying the composition into a heated atmosphere.

The firing process takes about 10 seconds to 1 hour at 170°C to 1000°C, and even at low temperatures of 190°C to 250°C, it takes about 5 to 30 minutes to form an amorphous film that is sufficiently strong and has good adhesion. can get.

You may dry at 100 degreeC - 250 degreeC before baking.

〔Effect of the invention〕

The first effect can be obtained by using the rare earth oxide thin film forming composition of the present invention.

1. The coating liquid is stable and easy to control during the coating process.

2. A transparent rare earth oxide thin film with high uniformity can be obtained.

3. By heating and spraying this composition liquid.

Powdered rare earth oxides can be obtained.

[Embodiment]

Example I Nd(OC4H-)2(CHs C0CI(COO
A solution of Ct L ) dissolved in butanol to a neodymium oxide equivalent concentration of 0.3 and 8 Ilt% was placed on a Pyrex substrate at a rate of 300% using a spritzer/ml.
After spin coating at 0 rpm for 15 seconds, drying at 150° C. for 15 ml, and baking at 550° C. for 1 hour, transparent neodymium oxide films with film thicknesses of 60 and 900 thick, respectively, could be obtained.

Example 2 Sc (OCR(CH3)2 ) z (CH3COC
+(COCHl) as scandium oxide equivalent concentration 0.5
A transparent scandium oxide film is obtained by applying a solution dissolved in isopropyl alcohol to a concentration of 7% and 4w on a quartz tube by dip coating, drying for 30ml at 250°C, and baking at 1000°C for 1 hour. was completed.

Example 3 In order to form a film of yttrium oxide, scandium oxide, neodymium oxide, europium oxide, terbium oxide, and dysprosium oxide on the inner surface of a quartz tube,
CH)2)2(CH,C0CHCOCH3) (However, the old Y, Sc, Nd, Eu, Tb, Dy)
were dissolved in isopropyl alcohol to a concentration of 1 wt% in terms of oxide, and sprayed into a quartz tube heated to 600°C using dry oxygen or air as a carrier gas, and thermally decomposed on the wall surface. We were able to coat the inner surface of a quartz tube with an oxide film compatible with rare earth compounds.

Further, by continuing spraying, a powdered rare earth oxide was obtained.

Example 4 M (OC48s) 2 (CH
3coctlcoc)l, ) -(H is Y,
After immersing and stirring a solution in which La, Ce, Tb, Dy, 'i'b) were dissolved in isopropyl alcohol at a concentration of 2 wt% in terms of oxide, it was filtered and dried at 100 °C for 30 minutes. By firing at 70° C. for 1 hour, titanium oxide and zirconium oxide powders whose surfaces were covered with oxides corresponding to the respective rare earth compounds were obtained.

Examples 5-25. Comparative Examples 1 to 17 Each of the organic solvent solutions of rare earth compounds listed in Table 1 was
3000 on a Pyrex substrate using a spin coater.
rpm, after spinning for 15 seconds, 150'C15m1n
After drying, oxide films corresponding to each rare earth compound were obtained by firing at 550° C. for 1 hour.

Example 26 A 5% organic solvent solution of the rare earth compounds listed in Table 1 was pyrolyzed in a tubular furnace heated to 700"C under an oxidizing atmosphere to obtain particles with a particle size of 0.5 to 3 microns.
A rare earth oxide powder was obtained.

Procedural Amendment June 2, 1988 Commissioner of the Patent Office Black 1) Mr. Akio 1, Indication of Case 1988 Patent Application No. 104489 2, Title of Invention For forming rare earth metal oxide films and powders Composition 3 of
, Relationship to the case of the person making the amendment Patent applicant name (626) Mitsubishi Metals Co., Ltd. 4, Agent (164) Address 1-31-4-5 Honmachi, Nakano-ku, Tokyo Date of amendment order Voluntary 6; Number of inventions increased by amendment None 7, Subject of amendment Detailed explanation of the invention in the specification column 8, Contents of the amendment Table 1 on page 14 of the detailed description of the amendment is corrected as shown in the attached sheet.

Claims (1)

[Claims] 1. Represented by the general formula M(OR)_mY_n(I), M is at least one rare earth element, R is an alkyl group of C_1_-_1_0, and Y is represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) β-diketones represented by , where R^1 and R^2 are C_1_-_6 alkyl groups, and R^3 is hydrogen or C_1_-_6 alkyl groups , or a chelate coordination chosen from β-keto esters represented by the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (III) and where R^1, R^2, R^3 are as defined above child, m and n are each an integer of 1 or 2, and m+n
A composition for forming a film and powder of a rare earth oxide, which comprises a compound in which =3 and an organic solvent.